N-substituted-n-chlorocycloalkylthio urea

ABSTRACT

COMPOUND OF THE FORMULA   R-N(-R1)-CO-N(-R2)(-S-R3)   WHEREIN R AND R1 ARE HYDROGEN, ALKYL OF 1 TO 12 CARBON ATOMS SUBSTITUTED WITH 0 TO 4 HALOGEN ATOMS OF ATOMIC NUMBER 9 TO 35, CYCLOALKYL OF 3 TO 12 CARBON ATOMS SUBSTITUTED WITH 0 TO 4 HALOGEN ATOMS OF ATOMIC NUMBER 9 TO 35, ARYL OF 6 TO 12 CARBON ATOMS SUBSTITUTED WITH 0 TO 4 HALOGEN ATOMS OF ATOMIC NUMBER 9 TO 35, NITRO GROUPS OR ALKOXY GROUPS OF 1 TO 16 CARBON ATOMS; R2 IS ALKYL OF 1 TO 10 CARBON ATOMS SUBSTITUTED WITH 0 TO 4 HALOGEN ATOMS OF ATOMIC NUMBER 17 TO 35 , CYCLOALKYL OF 5 TO 10 CARBON ATOMS SUBSTITUTED WITH 0 TO 4 HALOGEN ATOMS OF ATOMIC NUMBER 17 TO 35; AND R3 IS EITHER   -CH&lt;(-CH2-(CH2)N-CH2-CH(-CL)-)   WHEREIN N IS AN INTEGER OF FROM 1 TO 8, OR (B) MONOCHLOROBORNYL. THE COMPOUNDS ARE HERBICIDES.

Patented Jan. 16, 1973 3,711,530 N-SUBSTlTUTED-N-CgLgEOCYCLOALKYLTHlO John W. Kobzina, Berkeley, Joseph F. Moore, Richmond,

and Gustave K. Kohn, Berkeley, Calif, assignors to Chevron Research Company, San Francisco, Calif. No Drawing. Filed July 14, 1970, Ser. No. 54,855

Int. Cl. C07c 119/00 US. Cl. 260453 R 7 Claims ABSTRACT OF THE DISCLOSURE Compound of the formula wherein R and R are hydrogen, alkyl of l to 12 carbon atoms substituted with to 4 halogen atoms of atomic number 9 to 35, cycloalkyl of 3 to 12 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 9 to 35, aryl of 6 to 12 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 9 to 35, nitro groups or alkoxy groups of 1 to 16 carbon atoms; R is alkyl of 1 to 10 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 17 to 35, cycloalkyl of 5 to carbon atoms substituted with 0 to 4 halogen atoms of atomic number 17 to 35; and R is either --CHGH2 C1- H-CH:

wherein n is an integer of from 1 to 8, or

(b) monochloronorbornyl.

The compounds are herbicides.

FIELD OF THE INVENTION The present invention is directed to N-substituted-N- chlorocycloalkylthio ureas, their method of preparation and their use as herbicides.

DESCRIPTION OF THE INVENTION The nreas of the present invention may be represented by the formula o Ni N R s-R wherein R and R (which may be the same or different) are hydrogen, alkyl of 1 to 12 carbon atoms optionally substituted with halogen atoms of atomic number 9 to 35 (fluorine, chlorine or bromine), cycloalkyl of 3 to 12 carbon atoms optionally substituted with halogen atoms of atomic number 9' to 35, aryl of 6- to 12 carbon atoms optionally substituted with halogen atoms of atomic number 9 to 35, nitro groups or alkoxy grOups individually having 1 to 6 carbon atoms; R is alkyl of 1 to 10 carbon atoms optionally substituted with halogen atoms of atomic number 17 to 35, preferably 0 to 4 halogen atoms, cycloalkyl of 5 to 10 carbon atoms optionally substituted with halogen atoms of atomic number 17 to 35, preferably 0 to 4 halogen atoms; and R is either wherein n is an integer from 1 to 8, or (b) monochloronorbornyl.

R and R are preferably hydrogen, alkyl of 1 to 12, more preferably 1 to 4 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 9 to 35 (i.e., the alkyl may or may not be substituted with halogen atoms; if substituted the number of halogens will be from 1 to 4), cycloalkyl of 3 to 12 carbon atoms substituted with '0 to 4 halogen atoms of atomic number 9 to 35, aryl of 6- to 12 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 9 to 35, nitro groups or alkoxy groups wherein the alkyl portion is from 1 to 6 carbon atoms. Preferably, the total number of substituents on the aromatic nucleus of the aryl radical will not exceed 4.

Still more preferably in the above formula R represents phenyl; phenyl substituted with 1 to 4 halogen atoms of atomic number 9 to 35, nitro groups, alkyl groups individually of 1 to 4 carbon atoms or alkoxy groups individually of 1 to 4 carbon atoms, and R is hydrogen or alkyl of 1 to 4 carbon atoms optionally substituted with 0 to 4 halogen atoms of atomic number 9 to 35. Still more preferably R is hydrogen.

R is preferably alkyl of 1 to 6 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35, cycloalkyl of 5 to 6 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 17 to 35, preferably 1 to 2 halogen atoms of atomic number 17 to 35. Still more preferably R is alkyl of 1 to 4 carbon atoms substituted with 0 to 2 halogen atoms of atomic number 17 to 35, preferably chlorine.

R above as indicated may be either a chlorocycloalkyl group wherein n is an integer of from 1 to 8 and more preferably of from 1 to 4 and still more preferably of from 1 to 2 or a monochloronorbornyl group.

Representative groups which R and R may represent include hydrogen, methyl, ethyl, n-propyl, isopropyl, r1- butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, chloromethyl, bromomethyl, 1,2-dichloroethyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, chlorocyclohexyl, fiuorocyclohexyl, phenyl, naphthyl, biphenyl, chlorophenyl, bromophenyl, fiuorophenyl, 2,2-dichlorophenyl, 4-chlorophenyl, 2-fluoro-4-chlorophenyl, 2- nitrophenyl, 2,4-dinitrophenyl, methoxyphenyl, ethoxyphenyl, fluoronaphthyl, chloronaphthyl, etc.

Representative R groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Z-methylbutyl, S-methylpentyl, chloromethyl, bromomethyl, 1,2-dich1oroethyl, cyclopentyl, cyclohexyl, etc.

Representative R groups are 3-chlorocyclopentyl, 2- chlorocyclohexyl, 2-chlorocyc1ooctyl, 2-chlorocyclododecyl, and monochloronorbornyl.

Representative compounds of the present invention include N-methyl-N-(Z-chlorocyclopentylthio) urea, N-methyl-N-(Z-chlorocyclopentylthio)-N-methyl urea, N-methyl-N- 2-chlorocyclopentylthio) -N-dimethyl urea, N-methyl-N-(2-chlorocyclopentylthio)- I-ethyl-N'- methyl urea, N-methyl-N-(Z-chlorocyclopentylthio)-N-n-butyl urea, N-methyl-N-(Z-chlorocyclopentylthio)-N'-n-hexyl urea, N-methyl-N-(2-chlorocyclopentylthio)-N'-2-methylhexyl urea, N-methyl-N-(Z-chlorocyclopentylthio)-N-phenyl urea, N-methyl-N-(Z-chlorocyclopentylthio)-N'- naphthyl urea, N-methyl-N-(2-chlorocyclopentylthio)-N'-2-fluoromethyl urea, N-methyl-N- (2-chloro cyclopentylthio) -N'-2chlorophenyl urea, N-methy1-N-( 2-chlorocyclopentylthio)-N'-3-chlorophenyl urea,

3 N-methyl-N- (Z-chlorocyclopentylthio -N'-4-nitrophenyl urea, N-rnethyl-N- (2-chlo'rocyclopentylthio N'-methoxyphenyl urea,

N-methyl-N-(Z-chlorocyclopentylthio)-N'-4-methoxyvents not miscible with water can also be used and include phenyl-N'-methyl urea, such compounds as ether, etc. Generally the solvent will N-methyl-N-(2-chlorocyclohexylthio)-urea, be present in an amount of 5 to 25 times the volume of N-methyl-N-(Z-chlorocyclohexylthio)-N-methyl urea, reactants. N-methyl-N-(2-chlorocyclohexylthio)-N-phenyl urea, For the reactions above, particularly for Step II, a hy- N-methyl-N-(Z-chlorocyclohexylthio)-N'-2-chlorodrogen halide acceptor is desirable preferably in at least phenyl urea, stoichiometric amounts to the HCl produced. When the N-methyl-N-(2-chlorocyclohexylthio)-N'-4-methoxyamine is an aromatic amine, it can be used in excess as a phenyl urea, basic acceptor for the HCl; however, this is generally not N-ethyl-N-(2-chlorocyclohexylthio) urea, practical. Other halogen halide acceptors are preferred N-ethyl-N-(2-chlorocyclohexylthio)-N'-phenyl urea, 1 h a triethyl amine or pyridine. N- hyl-N-( y y )-N'- -ni roph ny1 In the above reaction it is generally preferred that stoiufea, chiometric amounts of reactants be used. However in Step y '3'mtrophenyl' I the carbamoyl chloride may be present in less than the N methyl urea: equimolar amount and in Step II the amine may be pres- Nbutyl'N'(z'chiorocyclohexy%tgio) f i l ent in excess. However, it is generally desired that the g i g g g L 13 {33 cyclic or bicyclic reactant of Step I not be in excess of 1 ifi g fgg ig jaigggi zg fi g fi g mole per mole of other reactant and that the amine in urea y y y P y Step II not be in excess of 2.1 moles per mole of the other N-rnethyl-N-(2-chlorocycloheptylthio)-N-phenyl urea, reactant N-rnethyl-N-(Z-chlorocyclooctylthio)-N'- he y1 urea, Generally any amine chloride formed in the above re- N-methyl-N-(Z-chlorocyclononylthio)-N-phenyl ure action can be removed by filtration and excess solvent re- N-methyl-N-(2-chlorocyclodecylthio)N'-phenyl urea, moved under vacuum. The desired urea product of the N-methyl-N-(2-chlorocyclododecylthio)-N'-phenyl urea, present invention can then be purified by chromatography N-methyl-N-(monochloronorbornylthio)-N'-phenyl urea, or recrystallization from suitable solvents. N-methyl-N-(monochloronorbornylthio)-N'-2-flu0ro- It is difiicult to be precise as to the relative positions of P y urea, the chlorine and sulfur atoms attached to the norbornyl y y radical. As shown for Step I above, norbornylene is re- P y urea em acted with a carbamoyl chloride to produce the desired Compounds of the present invention may b prepared carbamate of the present invention. However, due to wellby the following reaction steps known possible multiple rearrangements under the condi- 2 2 /Cl-l (I) R if C Cl EH 2 n .9

SC]. H

Cl-l r H CH CH 2 II R i t c 01 s R (11) R N c c1 RR'NH l s R C N HCl R s R A solvent will generally be used for the above reaction. Benzene is particularly suitable, however, other solvents such as xylene and chlorinated hydrocarbons, e.g., methylene chloride or chloroform can be used. Aprotic soltions of the addition reaction of Step I, one of two possible monochloronorbornyl groups, or a mixture thereof, is formed. Either 2-chloronorborn-7-yl (2-chlorobicyclo- [2.2.1]hept-7-yl) or 3-chloronorborn-2-yl (3-chlorobicyclo[2.2.1]hept-2-yl) or a mixture of the two can be the resulting R group. For convenience of expression, the term monochloronorbornyl is used to describe either of the two possible structures or their mixture.

The carbarnoyl chlorides which are used as. reactants in Step I are made by the reaction of isocyanate and SCI in accordance with the following reaction:

wherein R is the same as defined above. The sulfur dichloride/isocyanate molar ratio should be at least 1:1. The sulfur dichloride is preferably present in excess. For best results it is necessary that the sulfur dichloride be in excess of 95%, preferably 99%, pure.

The reaction can be accomplished in the presence of a suitable inert organic solvent or neat. Preferably the solvent is low boiling and easily removed by a low tem- EXAMPLE 2 Preparation of N-methyl-N-(monochloronorbornylthio)- N'-(4-chlorophenyl) urea p f pp f p EXamPIeS of Suitable g. of N-methyl-N-chlorothio carbamoyl chloride vents include: dichloromethane, dlethylether, tetrahydrowas dd at 0 C to 1 f 2 1 2 2 n furfln aI 1d dlmethylfllfal (norbornylene) in 50 ml. of benzene and the reaction Suificrent solvent is used to dissolve the reactants. In mixture Stirred f 11 hours at 0 C 32 f 4 1 genera-1 1t 15 Sufiiclent t0 l about to 200 1111' of aniline and 150 ml. of benzene was then added dropwise solvent f each 01 111018 lsocyanate- Preferably 50 to 20 and the mixture stirred for 20 hours at room temperature. 100 1111-13 The aniline-hydrochloride precipitate was removed by The reactloll of i lsocyanate and Sulfur dlchlorlde 1S filtration and the filtrate washed twice with 50 ml. portions pfeffirably accompllshed 1n h P 9 9 of a Sultable of 5% hydrochloric acid and then once with 50 m1. of Catalyst, SuCh aS for exefnllfle iy 1111 9 tetra water. The washed solution of product was dried over ethyl ammomllm Chloflde and m y Tile P 25 magnesium sulfate and filtered and the solvent then referred calalyst tetfaethylammoPlum chlorlde- Althsugh moved under vacuum. The product after being recrystalthe reaction Will also proceed without the presence of a lized fr hl f t l ether had a melting catalyst, a catalyst is preferred. Generally about 1% to point f 79 g C and had the f ll wi chemical 50% by weight of catalyst based on isocyanate is suffianalysis; cient. Preferably the catalyst is removed before isolation Calculated (percent); 1 2054; S 9 9; N, s p of the carbamoyl chloride product or before in situ F d er ent): Cl, 19.50; S, 8.93;N,7.76, 1 reaction with a suitable reactant to produce the herbicidal o h urea compounds f the present invention were product described further hereinafter. prepared generally by the methods of Examples 1 and 2 The reaction is preferably accomplished at a temperaand are reported in Table I.

TABLE I Element analysis, percent Cl 8 N Melting Cale. Found Gale Found Cale. Found point, 0.

N-methyl-N-(2-chloroeyclohexylthio)-N-(2flu0r0phenyl) urea 11. 19 11.18 10. 12 9. 28 Oil N-rnethyl-N-(2-ch1orocyc1ohexylthio) urea 15. 85 15. 70 14. 33 14. 55 12. 52 11.68 108 N-methyl-N-(2-chlorocyelohexylthio)-N-phenyl urea 11. 86 9. 72 10. 35 10. 11 Oil N-methyl-N-(2-chlorocyelohexylthio)-N,N-dimethyl urea 14.14 13.50 12.78 11. 95 011 N-methyl-N-(Zchloroeyclohexylthio)-N-(4 methylphenyl) urea. 11. 33 11. 10. 25 10. 03 8. 95 8. 92 78 N-methyl-N-(2-chlorocyclohexy1thio)-N-(4-methoxyphenyl) urea 10. 78 10. 42 9. 75 9. 81 8. 52 8. 42 71-73 N-n-butyl-N-(2-chlorocyclohexylthio)-N-(4-chlorophenyl) urea- 8. 8. 87 18.90 19. 7. 50 6.12 Oil N-methyl-N-(2-chlorocyelopentylthio)-N-(4-chlorophenyl) urea- 22. 21 22. 00 10. 04 9. 93 8. 77 8. 34 49 N-methyl-N-(monochloronorbornylthio) urea 15. 10 15. 0O 13. 66 13. 35 11. 94 11.28 128-131 N-methyl-N-(monochloronorbornylthio)-N-(4-methylphenyl) urea" 10.91 8. 93 9. 87 9. 42 8. 62 8. 38 59-61 N-methyl-N-(monoehloronorbornylthio)-N-phenyl urea 10. 59 9. 75 9. 58 10. 16 0 ture of from 50 to 100 C. and at ambient or autog- UTILITY EXAMPLE 1 Preparation of N-rnethyl-N-(2-chlorocyclohexylthio)-N'- (4-chlorophenyl) urea 5 ml. of N-methyl-N-chlorothio carbamoyl chloride was added to 33 ml. of cyclohexene and cooled in ice. The reaction mixture was stirred several hours, then the excess cyclohexene removed under vacuum. The resultant carbamoyl chloride product was diluted with 10 m1. of benzene, then 8 g. of 4-chloroaniline and 105 ml. of benzene were added and the reaction mixture stirred overnight at room temperature. Following removal of the aniline hydrochloride by filtration, the filtrate was washed The ureas of the present invention are, in general, herbicidal in both preand post-emergence applications. For pre-emergence control of undesirable vegetation these ureas will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergence applications the ureas of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

Preand post-emergence herbicidal tests on representative ureas of this invention were made using the following method:

Pre-emergence test An acetone solution of the test ureas was prepared by mixing 750 mg. urea, 220 mg. of a nonionic surfactant and 5 ml. of acetone. This solution was added to approximately ml. of water containing 156 mg. of surfactant.

Seeds of the test vegetation were planted in a pot of soil and the urea solution was sprayed uniformly onto the 7 soil surface at a dose of 100 mg. per cm. The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the end of this period the herbicidal etfcctiveness of the urea was rated based on the physiological observations. A to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.

Post-emergence test The test urea was formulated in the same manner as described above for the pre-emergence test. The concentration of the urea in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 replicate pots of 24-day-old plants (approximately to 25 plants per pot) at a dose of 100 mg. per cm. After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed.v The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal efiectiveness of the urea was rated based on these observations. A 0 to 100 scale was used; 0 representing no phytotoxicity, 100 rep resenting complete kill.

The results of these tests appear in Table II.

without departing from the spirit or scope of the disclosure or from the scope of the following claims.

We claim:

1. Compound of the formula wherein R is phenyl, phenyl substituted with halogen 10 atoms of atomic number 9 to 35, nitro groups, alkyl (b) monochloronorbornyl selected from 2 chloronorborn-7-yl, 3-chloronorborn-2-yl or a mixture thereof. 2. The compound of claim 1 wherein R is hydrogen. 3. The compound of claim 2 wherein R ismethyl. 4. Compound of claim 2 wherein n is an integer of from 1 to 2.

TAB LE II Herbicidal effectiveness, pre/post Compound 0 W C M P L 0 N-methyl-N-(2-ehlorocyelohexylthio) -N-(4-chlorophenyl) urea 98/100 100/100 99/100 100/100 100/100 100/100 N-meth yl N(2-elilorooyclohexylthio) -N-(2-fluorophenyl) urea X 100/100 98/95 90/83 08/1 00 100/100 95/100 N-methyl-N-(Z-chlorocyclohexylthi0) urea 15/ /20 /20 N-methyl-N-(2-chloroeycl0hexylthio)-N-phenyl urea 100/93 100/85 100/79 100/100 100/100 100/100 N-methy1-N-(2-chlorocyclohexylthio)-N,N-dimethyl urea 20 33/ /40 2O N-methyl-N-(2chlorocyeloh exylthio) -N-(4-Inethylphenyl) urea 100/ 85 100/ 100/30 100/ 95 100/100 100/100 N-methyl-N-(2-cliloroeyelohexylthio) -N(4-methoxyphenyl) urea 96/35 98/25 100/ 100/ 100/90 100/ N-n-butyl-N-(2-eh1orocyol0hexylthio) -N-(4 chlorophenyl) urea.-. 30/95 67/ 37/100 67/100 N -methyl-N-(2-0hl0rocycl opentylthio) -N -(4-ehlorophenyl) urea 100/100 100/100 100/100 100/100 100/100 100/100 Nqnethyl-N-(monoohloronorb ornylthio) -N-(4ohlorophenyl) uream. 50/100 97/100 97/100 100/ 100/100 100/10/ N-rnetllyl-N-(monochloronorbornylthio) urea 37 27/ 30/ 57/ 430 N-rnethyl-N-(monochloron orb ornylthio) -N-(4-mcthylphenyl) urea. 33/100 33/100 100/100 98/100 100/100 100/100 N-methyl-N-(monochloronorbornylthio) -N -phenyl urea 100/ 83 98/ 100/ 100/08 100/ 70 96/10 1 33 micrograms/cm. application.

N0rE.--O=Wild oats (Aurma fatua); W=Watergrass (Echinochloa crusgalli): O=Crabgrass (Digituria sanguinalis); 1WI=1WIustard (Brassica arwmsz's); P=Pigweed (Amaranthus retroflezus); L=Larnbsquarter (Clwnopodium album The amount of urea administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application, i.e., sheltered areas such as greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pro-emergent control of most plants dosages in the range of about 0.5 to 20 lbs. per acre will be used. Such administration will give a concentration of about 2 to 80 p.p.m. urea distributed throughout 0.1 acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. urea per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. urea per acre.

The herbicidal compositions of this inventon comprise a herbicidal amount-of one or more of the above described ureas intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also 60 5. Compound of claim 2 wherein 'R is phenyl substituted with 1 to 4 halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbon atoms.

6. Compound of claim 2 wherein R is 4-chlorophenyl,

45 R is methyl and n is an integer of from 1 to 2.

7. The compound of claim 1 wherein R is 2-fluorophenyl, R is hydrogen, R is methyl and n is 2.

References Cited UNITED STATES PATENTS 3,496,208 2/1970 Bachman 61: al. 260-453 R 3,502,705 3/1970 Brown 260-453 R 3,234,275 2/1966 MalZ et al. 71-98 55 3,344,153 9/1967 Kuhle 61; a1 260-453 R 3,347,658 10/1967 Luckenbaugh 71 119 3,351,457 11/1967 Luckenbaugh 71- 120 3,352,662 11/1967 Klopping et al. 71- 120 3,124,447 3/1964 Wineman et al. 71-103 3,652,630 3/1972 Brown 71-67 FOREIGN PATENTS 303,072 1/1 s9 Great Britain 260--56 A LEWIS GOTTS, Primary Examiner 5 G. HOLLRAH, Assistant Examiner US. Cl. X.R. 7l-98; 260-543 A 

